TWI431639B - Conductive film - Google Patents

Description

Conductive film

The present invention relates to a conductive film. More specifically, it is a transparent conductive film which is excellent in transparency and electrical conductivity and is excellent in moisture resistance.

A transparent conductive film is used as a transparent electrode or an electromagnetic wave sealing material of a liquid crystal display device, a transparent touch panel, or the like.

The transparent conductive film is made of indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), or the like on the surface of a transparent film such as polyethylene terephthalate (PET) or triethylenesulfonyl cellulose (TAC). It is known that a mixed sintered body of In ₂ O ₃ and SnO ₂ (ITO) or the like is provided by a ruthenium process such as a vacuum deposition method, a sputtering method, or an ion coating method.

Further, it is known that a wet process which forms a coating layer by coating a conductive polymer on the surface of a transparent film is used as a transparent conductive film. The conductive polymer used in the wet process is known as polythiophene, polyaniline, polypyrrole or the like.

Since the transparent conductive film is subjected to continuous processing in a fiber web shape, subjected to a perforation treatment, and subjected to surface processing and storage treatment in a bent state, the transparent conductive film obtained by the 亁-type process is produced during processing or storage. A condition in which the crack is broken and the surface resistance is increased.

Further, the transparent conductive film formed by the wet process has a problem that the film layer itself has flexibility and is less likely to cause cracking or the like. Moreover, when the wet process is compared with the 亁 process, the manufacturing cost is low and the coating speed is faster than usual, so that the productivity is excellent. However, the transparent conductive film by a wet process has a drawback that conductivity and color are not equal enough.

In recent years, various improvements have been proposed regarding a transparent conductive film by a wet process. For example, a conductive polymer formed by poly(3,4-dialkoxythiophene) obtained by oxidative polymerization of 3.4-dialkoxythiophene in the presence of a polyanion and a polyanion (Patent Document 1) According to the improvement method (Patent Document 2 and Patent Document 3), etc., it is possible to have a very low surface resistance while maintaining a high light transmittance.

However, the conductive film using such a conductive polymer as the film layer has a disadvantage of poor heat and humidity resistance, and is insufficient for use in a liquid crystal display device (LCD) transparent touch panel or the like. Therefore, in order to improve the water resistance of the conductive polymer, various methods of using various binders have been proposed (Patent Document 4).

(Patent Document 1) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin

An object of the present invention is to provide a conductive film which is excellent in moisture and heat resistance even when it is used for a display device electrode or a touch panel electrode. Further, the present invention provides a conductive film which is excellent in conductivity, transparency, and film strength.

In the conductive film containing polythiophene in the film layer, when the film layer contains a water-soluble compound, conductivity can be improved. However, when a water-soluble compound is contained, the heat resistance of the electroconductive film is lowered. The inventors of the present invention reviewed a method for making both the conductivity and the moist heat resistance of the film. As a result, it has been found that when polythiophene and a water-soluble compound are added to the coating layer and a crosslinking agent is contained, the heat and humidity resistance can be improved while maintaining conductivity, and the present invention has been completed.

In other words, the present invention relates to a conductive film characterized in that (i) a polycationic polythiophene containing a polycation-containing repeating unit represented by the following formula (1) is laminated on at least one side of a base film. Polyanion conductive polymer (component A),

In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or an alkylene group having 1 to 12 carbon atoms which may be optionally substituted, and (ii) 100 parts by mass of A. 10 to 1,000 parts by mass of the water-soluble compound (component B) having at least one hydrophilic group selected from the group consisting of oxyethylene groups and sulfonate groups, and (iii) 10 to 1,000 parts by mass for 100 parts by mass of the component A The coating layer having a composition of a crosslinking agent (component C) of a glycidyl group is cured at a temperature of 60 ° C and a humidity of 90% for 240 hours, and the rate of change in surface resistance is 160% or less.

In addition, the present invention relates to a touch panel which is characterized in that at least one electrode is formed in a resistive film type touch panel in which a pair of conductive layers are disposed via a spacer and a conductive layer is disposed opposite to each other. The above conductive film is used.

[In order to implement the best form of the invention]

First, the conductive film of the present invention will be described using the drawings. Fig. 1 is a cross-sectional view showing a conductive film of the present invention, which is an example of a layer configuration. In Fig. 1, reference numeral 1 denotes a base film, reference numeral 2 denotes a tackifying coating layer which is required to be provided, reference numeral 3 denotes a film layer, and reference numeral 4 denotes a hard coating layer which is required to be provided. As is apparent from Fig. 1, the conductive film of the present invention is a layer on which a film layer is laminated on at least one surface of a base film as desired. In the case of such a configuration, for example, other functional layers such as a hard coating layer can be formed without impairing the object of the present invention, and the first (b) diagram is provided with a tackifying coating on the opposite side to the surface on which the coating layer is formed. And examples of hard coatings. In the conductive film of the present invention, a film layer formed of the following composition is laminated on at least one surface of the base film. The conductive film according to the present invention will be described in more detail below.

The conductive film of the present invention is a conductive film in which a film layer is laminated on at least one surface of a base film. The film layer of the present invention is a layer obtained by curing a composition containing a conductive polymer (component A), a water-soluble compound (component B), and a crosslinking agent (component C).

(conductive polymer: component A)

The conductive polymer (component A) contains a polycationic polythiophene (poly 3,4-disubstituted thiophene) mainly composed of a unit represented by the following formula (1), and a polyanion. In other words, the conductive polymer (component A) is a composite compound of polythiophene and polyanion. The conductive polymer (component A) is a dispersion liquid dispersed in water.

In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. An alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group.

Further, R ¹ and R ² are bonded to each other to represent an optionally substituted alkylene group having 1 to 12 carbon atoms. An alkylene group having 1 to 12 carbon atoms, such as methylene, 1,2-extended ethyl, 1,2-extended propyl, 1,3-propanyl, 2,3-butylene, 2,3 - pentyl group, 1,2-cyclohexyl group, and the like. In particular, a 1,2-alkylene group such as a methylene group and a 1,2-extended ethyl group or a 1,2-cyclohexyl group is preferred. The 1,2-alkylene group is, for example, a 1,2-dibrominated alkane obtained by brominating an α-olefin such as ethylene, propylene, hexene, octene, decene, dodecene or styrene. Derived from the class. The substituent is, for example, an alkyl group having 1 to 12 carbon atoms or a phenyl group. The alkyl group having 1 to 12 carbon atoms of the substituent, such as a methyl group, an ethyl group, a propyl group or the like.

"Main" means that the unit of the formula (1) is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, and more preferably 90 to 100% of the repeating unit constituting the polythiophene. 100% of the best. Other repeating units, for example, repeating units having no substituents OR ¹ and/or OR ² in formula (1).

The polythiophene having a repeating unit represented by the formula (1) is a cationic one. The polythiophene having such a cationic property can be obtained by oxidative polymerization of a monomeric 3,4-disubstituted thiophene, for example, by the method described in JP-A-01-313521.

The polyanion is, for example, a polymer carboxylic acid or a polymer sulfonic acid. A polymer carboxylic acid such as polyacrylic acid, polymethacrylic acid, polymaleic acid or the like. A polymer sulfonic acid such as polystyrene sulfonic acid or polyvinyl sulfonic acid.

Further, the polyanion such as a polymer carboxylic acid or a polymer sulfonic acid may be a homopolymer polymerized only from an anionic monomer such as a vinyl carboxylic acid or a vinyl sulfonic acid. Further, it may be a copolymer composed of a plurality of anionic monomers. Further, it may be a copolymer of an anionic monomer and other monomers copolymerizable with the monomer. Other monomers copolymerizable with anionic monomers, such as acrylates, styrene, and the like.

When the polyanion is a copolymer, at least one anionic monomer may be contained as a copolymer component, and a plurality of anionic monomers or a plurality of other copolymerizable monomers may be optionally used.

Among these, the polyanion is more preferably polystyrenesulfonic acid and at least partially a metal salt. The number average molecular weight of the polyanion is preferably from 1,000 to 2,000,000, more preferably from 2,000 to 500,000.

The content of the anionic monomer constituting the polyanion in the conductive polymer (component A) is preferably 0.1 in terms of the repeating unit represented by the formula (1) for the 1 mol of the 3,4-disubstituted thiophene. ~20% by mole, more preferably 0.25~10% by mole, and the best is 0.5~5% by mole.

(water-soluble compound: component B)

The water-soluble compound (component B) has at least one hydrophilic group selected from the group consisting of oxyethylene groups and sulfonate groups. The content of the water-soluble compound (component B) is 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the conductive polymer (component A).

(B-1 component) a water-soluble compound (component B) containing three or more photocurable functional groups and oxyethylene groups (-O-CH ₂ -CH ₂ -) in a molecule, and the total number of oxyethylene groups The water-soluble compound (component B-1) of 10 to 30 is preferred.

The photocurable functional group is, for example, an acrylic group, a methacryl group, an epoxy group or an oxetanyl group, and among them, an acrylic group and a methacryl group (hereinafter collectively referred to as a (meth)acryl group) are preferred. When the number of photocurable functional groups in the component B-1 is 2 or less, the crosslinking density after curing is insufficient, and the effect of improving the moist heat resistance is also insufficient. Further, the upper limit of the number of photocurable functional groups is not particularly limited, and generally 6 or less is used for availability or cost.

In order to carry out the crosslinking reaction/hardening of the photocurable functional group, it is preferred to contain a photopolymerization initiator. Photopolymerization initiators such as 1-hydroxycyclohexyl benzophenone, 2,2-dimethoxy-2-phenylacetophenone, thioxanthone, acetone, anthrone, benzaldehyde, anthracene, anthrone, triphenylamine, Carbazole, 3-methylacetophenone, 4-benzoic benzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1-1 [4-(A Thio)phenyl]-2-morpholine-1-propan-1-one, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis-(2,6-dimethoxy Benzobenzyl) 2,4,4-trimethylpentylphosphine oxide, and the like. The content of the photopolymerization initiator is preferably 10 parts by mass or less per 100 parts by mass of the water-soluble compound (B-1). When the amount is more than 10 parts by mass based on 100 parts by mass of the B-1 component, the strength of the coating layer may be lowered when the photopolymerization initiator is used as the plasticizer.

The total number of oxyethylene groups is preferably from 10 to 30, more preferably from 15 to 25. The oxyethylene group may also be concentrated in one molecule in the molecule, but it is preferably divided into 2 to 4 places. Further, when the total number of oxyethylene groups in the component B-1 is less than 10, the water solubility is insufficient, and the stability of the composition is deteriorated. On the other hand, when the ratio is more than 30, the molecular weight of the component B-1 is too large, and the crosslinking density is lowered. As a result, the effect of improving the moist heat resistance is insufficient. The component B-1 is, for example, a compound represented by the following formulas (2) to (4).

In the formulas (2) to (4), l, m, n, and o are integers of 0 or more. In the compound represented by the formula (2), l+m+n is preferably from 10 to 30, more preferably from 15 to 25. In the compound represented by the formula (3), l+m+n is preferably from 10 to 30, more preferably from 15 to 25. In the compound represented by the formula (4), l+m+n is preferably from 10 to 30, more preferably from 15 to 25.

The content of the B-1 component is 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the conductive polymer (component A).

(Component B-2) The water-soluble compound (component B) is preferably a water-soluble polyester (component B-2) having a sulfonate group and a hydroxyl group or a carboxyl group.

The component B-2 is a polyester formed of a dicarboxylic acid component and a diol component. The dicarboxylic acid component is, for example, terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid metal salt or the like. The diol component is, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl alcohol, cyclohexanedimethanol or the like. The component B-2 is produced by polycondensing a dicarboxylic acid with a diol.

The weight average molecular weight of the water-soluble polyester (component B-2) is preferably from 1,000 to 100,000, more preferably from 10,000 to 50,000.

The component B-2 contains a sulfonate group. The B-2 component is, for example, an alkali metal salt of a sulfonic acid represented by -SO ₃ Na or -SO ₃ K. The content of the sulfonate group in the component B-2 is preferably from 2 to 10 mol%, more preferably from 5 to 8 mol%, based on the total acid component of the 100 mol% B-2 component. . The B-2 component contains 65 to 85 mol% of terephthalic acid, 10 to 27 mol% of isophthalic acid, and 5 to 8 mol% of 5-sulfophthalic acid base as the dicarboxylic acid component. Metal salts are preferred.

The component B-2 contains a hydroxyl group, a carboxyl group or both. The total content of the hydroxyl group and the carboxyl group is preferably from 0.1 to 40 mol%, more preferably from 1 to 20 mol%, based on the total acid component of the 100 mol% B-2 component. The hydroxyl group or the carboxyl group may be at both the terminal or side chain, or may be used on either side, and the number thereof is not limited. The "water-soluble" of the present invention means a substance which is soluble in methanol containing 50% by volume or more of water.

Commercially available products can also be used as the B-2 component. Commercially available water-soluble polyesters, for example, manufactured by Mutual Chemical Co., Ltd., trade names: Blasqueton RZ-570, RZ-142, Z-565, Z-561, Z-685.

The content of the component B-2 in the composition is preferably 25 to 55 parts by mass, more preferably 30 to 55 parts by mass, and most preferably 35 to 55 parts by mass, per 100 parts by mass of the conductive polymer (component A). good. When the content of the component B-2 is less than 25 parts by mass based on 100 parts by mass of the component A, the moist heat resistance is insufficient. Further, when the content is more than 55 parts by mass, the electrical conductivity is lowered. In addition, "for 100 parts by mass of the conductive polymer" as used herein means "for 100 parts by mass of the solid component of the conductive polymer".

(crosslinking agent: component C)

The crosslinking agent (component C) has a glycidyl group. The content of the component C is 10 to 1,000 parts by mass based on 100 parts by mass of the conductive polymer (component A).

(C-1 component) The crosslinking agent (component C) is preferably an alkoxysilane having a glycidyl group (component C-1). The component C-1 is preferably a trialkoxy decane having a glycidoxy group. For example, gamma-glycidoxypropyltrimethoxydecane.

In order to carry out the hydrolysis/condensation reaction of the alkoxydecane more efficiently, it is preferred to use a catalyst in combination. The catalyst can be either an acidic catalyst or an alkaline catalyst. The acid catalyst is an inorganic acid such as acetic acid, hydrochloric acid or nitric acid, an organic acid such as acetic acid, citric acid, propionic acid, oxalic acid or p-toluenesulfonic acid. Further, the basic catalyst is an organic amine compound such as ammonium, triethylamine or tripropylamine, or an alkali metal compound such as sodium methoxide, potassium methoxide, potassium ethoxylate, sodium hydroxide or potassium hydroxide.

The content of the component C-1 is 10 to 1,000 parts by mass, preferably 20 to 300 parts by mass, and more preferably 30 to 200 parts by mass, per 100 parts by mass of the conductive polymer (component A). When the content of the component C-1 is less than 10 parts by mass, the strength, moisture resistance, and solvent resistance of the obtained coating layer are lowered, and when the amount is more than 1,000 parts by mass, the conductivity of the obtained coating layer is lowered, so that it is not desired. .

By using the component C-1, the heat resistance and strength of the coating layer can be improved. The alkoxydecane compound is present in the coating layer in the form of a reaction product formed by hydrolysis and further by a condensation reaction.

(C-2 component) The crosslinking agent (component C) is preferably an acrylic modified polyester (C-2 component) having a glycidyl group. The component C-2 can be crosslinked by itself and contains a hydroxyl group or a carboxyl group of the water-soluble polyester (component B-2), and has a function as a crosslinking agent. By the component C-2, a film having high heat and humidity resistance can be obtained. The C-2 component is stable even in the coating liquid under acidic conditions, and can be used for a long period of time.

The position of the epoxy propyl group of the component C-2 is not particularly limited and may be either at the end or the side chain, or may be on either side. The content of the epoxy propyl group is preferably from 3 to 20 mol%, more preferably from 5 to 15 mol%, to the acrylic component of 100 mol% of the C-2 component.

The C-2 component can be produced by the method described in JP-A-63-37937 and JP-A-11-198327. In other words, a polyester copolymer is used as a dry polymer, and an acrylic copolymer as a branch polymer is graft-polymerized and produced thereon. When graft polymerization is carried out, (A) a reaction initiation point for generating a radical, a cation or an anion in a dry polymer, a graft polymerization of an acrylic monomer, and (B) in the presence of a dry polymer, A method of graft-polymerizing an acrylic monomer by a chain reaction reaction of the polymer, (C) a dry polymer having a functional group in a side chain and a branch polymer having a group reactive with the above functional group at a terminal The method of carrying out the reaction, and the like.

The acrylic modified polyester has a graft copolymer in which an acrylic monomer is polymerized in the presence of a polyester, or a graft copolymer in which a polyester and an acrylic polymer are polymer-reacted. The polyester is a linear polyester having a polyvalent carboxylic acid component and a polyol component as a constituent component, and the polyvalent carboxylic acid component is, for example, terephthalic acid, isophthalic acid, sulfoisophthalic acid metal salt or naphthalene dicarboxylic acid. 4,4'-diphenyldicarboxylic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, hexahydroterephthalic acid and the like are preferred.

Further, the polyol component is, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl alcohol, 1,5-pentanediol, 1,6-hexane Alcohol, dipropylene glycol, triethylene glycol, bisphenol A-oxyalkylene adduct, hydrogenated bisphenol A-oxyalkylene adduct, 1,4-cyclohexanedimethanol, polyethylene glycol , polytetramethylene glycol, etc. are preferred

In order to impart hydrophilicity to the polyester, the component having a sulfonate group can be copolymerized. In order to make the polyester resin hydrophilic, the dispersibility in the aqueous coating liquid is good. This component is, for example, 5-Nasulfoisophthalic acid, 5-Ksulfoisophthalic acid or the like.

The polyester may be a copolymerized in a small amount (for example, 5 mol% or less) in a range in which a trifunctional or higher polyvalent compound is substantially formed into a linear polymer. The trifunctional or higher polyvalent compound, for example, trimellitic acid, pyromellitic acid, dimethylolpropionic acid, glycerin, trimethylolpropane or the like.

Acrylic monomers used in the manufacture of graft copolymers, such as ethyl acrylate, methyl acrylate, acrylic acid, butyl acrylate, sodium acrylate, ammonium acrylate, ethyl methacrylate, methyl methacrylate, methacrylic acid , butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, methacrylamide, N-methoxymethyl propylene amide, N-methylol propylene Amidoxime and the like. Further, the acrylic polymer is, for example, a polymer or a copolymer of an acrylic monomer. Commercially available products can also be used as the C-2 component. A commercially available acrylic modified polyester, for example, manufactured by Takamatsu Oil Co., Ltd., trade name: Bensley A (Audio) A-615GE, A-613GX, A-614GL.

The number average molecular weight of the polyester component in the component C-2 is preferably from 500 to 50,000, more preferably from 1,000 to 30,000. The number average molecular weight of the acrylic component in the component C-2 is preferably from 500 to 50,000, more preferably from 1,000 to 30,000. The number average molecular weight of the entire C-2 component is preferably from 1,000 to 100,000, more preferably from 2,000 to 60,000.

The content of the component C-2 in the composition is preferably from 1 to 16 parts by mass, more preferably from 4 to 16 parts by mass, even more preferably from 8 to 16 parts by mass per 100 parts by mass of the conductive polymer (component A). . When the content of the component C-2 is more than 16 parts by mass, the conductivity of the film is lowered. In addition, the term "100 parts by mass of the conductive polymer" as used herein means "the solid content of 100 parts by mass of the conductive polymer" as described above.

(other ingredients)

The composition may also contain diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol or the like in order to improve the electrical conductivity. Further, it may contain a water-soluble compound having a guanamine bond in the molecule and being liquid at room temperature.

The content of the above-mentioned compound is preferably 10 to 1,000 parts by mass, more preferably 30 to 600 parts by mass, per 100 parts by mass of the conductive polymer (component A). When the content is less than 10 parts by mass, a sufficient effect of improving the electrical conductivity cannot be obtained, and as a result, the surface specific resistance value hardly decreases. In addition, when the content is more than 1,000 parts by mass, the haze value of the film is likely to increase, the transparency is lowered, and the strength of the film itself is lowered, and peeling is easily caused, and when the film is wound into a roll, the inside of the film is easily transferred. And so on.

In the film, the strength of the obtained film and the prevention of the conductive polymer (component A) from falling off the film, in addition to the epoxy-modified acrylic modified polyester (C-2 component), the organic polymer binder is contained. It is preferable as an arbitrary component. Organic polymer binders such as polyester, polyacrylic acid, polyurethane, polyvinyl acetate, polyvinyl butyral, and the like.

The film may also contain an antioxidant, a heat stabilizer, a weathering stabilizer, a UV absorber, an organic slip agent, a pigment, a dye, an organic or inorganic fine particle, a filler, a transparent conductive agent, within a range that does not impair the effects of the present invention. , nuclear agents, etc.

(covered composition)

The film can be formed by coating the coating composition. Here, the coating composition contains a conductive polymer (component A), a water-soluble compound (component B), a crosslinking agent (component C), other optional components, and water. The coating composition can be mixed and produced by stirring the components. In particular, when the ultrasonic treatment is performed and dispersed, the components can be uniformly dispersed.

In the coated composition, a suitable solvent compatible with the water of the dispersion medium may be added within a range allowed by the drying process. The solvent is, for example, methanol, ethanol, 2-propanol, n-propanol, isobutanol, ethylene glycol, acetone, acetonitrile, tetrahydrofuran, dioxane, and a mixed solvent thereof.

The organic polymer binder can be dissolved by a solvent. Moreover, the wettability to the substrate film can be improved. Further, the solid content concentration of the coated composition can be adjusted.

The coating composition may contain a small amount of a surfactant in order to improve the wettability to the base film. Preferred surfactants, such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, sorbitol fatty acid ester, etc., nonionic surfactants, fluorinated alkyl carboxylates, perfluoroalkylbenzenes A fluorine-based surfactant such as a sulfonate, a perfluoroalkyl quaternary ammonium salt or a perfluoroalkyl polyoxyethylene ethanol.

(substrate film)

The substrate film is made of (meth)acrylic resin, polystyrene, polyvinyl acetate, polyolefin such as polyethylene or polypropylene, polyvinyl chloride, polychlorinated vinylidene, polyimine, poly A film made of decylamine, polyfluorene, polycarbonate, polyester, or a resin modified with a functional group such as an amine group, an epoxy group, a hydroxyl group or a carboxyl group, or a triacetyl cellulose (TAC). should.

Polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate dicarboxylate (PEN), and the like. The polyester may be copolymerized with a third component having a total acid component of 20 mol% or less, preferably 10 mol% or less.

Among these base film, a copolymerized polyester film of PET, PEN or the like is more preferable in terms of mechanical properties, transparency, and production cost. The thickness of the base film is not particularly limited, and is preferably 500 μm or less. When it is thicker than 500 μm, the rigidity is too strong, and the rationality of the film obtained when it is attached to a display device or the like is easily lowered.

When a polyester film is used as the base film, the coating treatment of the aqueous coating liquid in the case of providing the following adhesion-promoting coating can be carried out at any stage. It is preferably implemented in the manufacturing process of polyester. In particular, it is preferred to coat the polyester film before the completion of the alignment crystallization.

Here, the polyester film before the completion of the alignment crystallization includes an unstretched film, a one-axis alignment film in which the unstretched film is aligned in either the longitudinal direction or the lateral direction, and is low in both the longitudinal direction and the transverse direction. The rate-aligning person (finally extending in the longitudinal direction and the transverse direction to complete the biaxially stretched film before the alignment crystallization) and the like.

Among them, the aqueous coating liquid is applied to form a tackifying coating on an unstretched film or a one-axis stretch film oriented in one direction, and it is preferable to directly perform longitudinal stretching and/or lateral stretching and heat fixing treatment.

When the base film is coated with the aqueous coating liquid when the adhesion-promoting coating layer is formed, the physical treatment such as corona discharge treatment, flame treatment, plasma treatment, or the like is applied to the surface of the film, or the composition is simultaneously used. It is preferred to use a chemically inert surfactant as a preliminary treatment for improving adhesion or coating properties.

The surfactant is used to promote the wettability of the aqueous coating liquid for forming the adhesion-promoting coating to the substrate film, such as polyoxyethylene alkyl phenyl ether, polyoxyethylene-fatty acid ester, sorbitol aliphatic ester, and C. An anionic, nonionic surfactant such as a triol fatty acid ester, a fatty acid metal soap, an alkyl sulfate, an alkyl sulfonate or an alkyl sulfosuccinate. The surfactant is preferably contained in the composition for forming the film in an amount of 0.1 to 10% by weight.

(Manufacturing method of conductive film)

The conductive film of the present invention can be produced by coating a coating film on a base film to form a film layer.

As the coating method for forming the coating layer, a method known per se can be employed. For example, the slit direct coating method, the vertical mold coating method, the slit reversible method, the mold coating method, the gravure roll coating method, the distributed coating method, the spray coating method, the air knife coating method, the dip coating method, the rod coating method, and the like are preferred. .

The coating layer can be coated with the coating composition, and after the coating layer is dried, it is cured. Drying can be carried out by heating. Hardening can be performed by heating, ultraviolet irradiation, electron beam irradiation, or the like. The heating condition is preferably carried out at 80 to 160 ° C for 10 to 120 seconds, more preferably at 100 to 150 ° C for 20 to 60 seconds. The amount of ultraviolet radiation is generally 10 ~ 2,000mJ / cm ^2, to 50 ~ 1,500mJ / cm ² preferably, to 100 ~ 1,000mJ / cm ² more preferably.

Further, when the coating composition is coated on the base film, physical surface treatment such as corona discharge treatment or plasma discharge treatment may be additionally performed as needed to further improve the adhesion. Prepared for coverage.

The thickness of the coating layer is preferably 0.01 to 0.30 μm, more preferably 0.02 to 0.25 μm. When the thickness of the coating layer is too thin, sufficient conductivity cannot be obtained. Conversely, when it is too thick, the total light transmittance is insufficient and adhesion is caused.

(adhesive coating)

In the present invention, an adhesion-promoting coating may be provided between the film layer and the substrate film as needed. The component for forming the tackifying coating layer is transparent as long as it is a polyurethane resin, a polyacrylate resin, a polyester resin, a polyvinylpyrrolidone resin, a polyvinyl alcohol, a polyvinyl alcohol/polyethylene copolymer, or the like. Sex is OK, there are no special restrictions.

The adhesion-promoting coating layer is preferably an acrylic resin (Q) having a polyester resin (P), an oxazoline group, and a polyoxyalkylene chain in terms of adhesion.

The polyester resin (P) used herein is, for example, a polyester composed of a polybasic acid and a polyol shown below. Particularly preferred are polyesters which have solubility or dispersibility in water (and possibly some organic solvents).

Polybasic component of polyester resin (P), such as terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer acid, 5-sodium sulfoisophthalic acid, and the like. Among them, a copolymerized polyester containing two or more of these acid components is preferred. Further, a small amount of an unsaturated polybasic acid component such as maleic acid or itaconic acid or a hydroxycarboxylic acid component such as p-hydroxybenzoic acid may be contained.

Further, a polyol component such as ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, benzenedimethanol, dihydroxyl Methylpropane or the like, or (oxyethylene) alcohol, poly(tetramethylol) alcohol.

Further, an acrylic resin (Q) having an oxazoline group and a polyoxyalkylene chain is preferred as an acrylic resin having solubility or dispersibility in water (and possibly some organic solvent). The acrylic resin (Q) having an oxazoline group and a polyoxyalkylene chain, for example, contains a monomer shown below as a copolymerization component.

First, a monomer having an oxazoline group, such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2 - oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and the like. These may be used alone or in combination of two or more. Among them, 2-isopropenyl-2-oxazoline is preferred in the industry. By using the oxazoline group-containing acrylic resin, the cohesive force of the adhesion-promoting coating layer can be improved and the adhesion to the coating layer can be made stronger. Further, the metal roll for the film forming process and the film forming process can impart scratch resistance to the base film. Further, the content of the oxazoline group-containing monomer is preferably from 2 to 40% by weight in the acrylic resin (Q), more preferably from 3 to 35% by weight, still more preferably from 5 to 30% by weight.

Next, a monomer having a polyoxyalkylene chain, for example, an oxyalkylene group is added to a carboxyl group at the carboxyl group of acrylic acid or methacrylic acid. Polyoxyalkylene chains such as polyethylene oxide, polypropylene oxide, polybutylene oxide, and the like. The repeating unit of the polyoxyalkylene chain is preferably from 3 to 100. By using the acrylic resin (Q) having an oxyalkylene chain, the compatibility of the polyester resin (P) with the acrylic resin (Q) in the adhesion-promoting coating, and the acrylic resin not containing the polyoxyalkylene chain Better in comparison to improve the transparency of the adhesion-promoting coating. Here, when the repeating unit of the polyoxyalkylene chain is less than 3, the compatibility of the polyester resin with the acrylic resin is lowered, and the transparency of the tackifying coating is lowered, and conversely, when it is greater than 100, the heat resistance of the tackifying coating is lowered. The adhesion between the transparent conductive film layer and the high-humidity and high-temperature is deteriorated. Further, the content of the monomer having a polyoxyalkylene chain is from 3 to 40% by weight, preferably from 4 to 35% by weight, more preferably from 5 to 30% by weight, based on the amount of the acrylic resin (Q). range.

Other copolymerized components of the acrylic resin (Q), such as the monomers described below. In other words, alkyl acrylate, alkyl methacrylate (alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 3-butyl, 2-ethylhexyl, ring Hydryl group, etc.): hydroxyl group-containing monomer such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc.; An epoxy group-containing monomer such as acrylate, glycidyl methacrylate or allyl epoxidized ether; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, a monomer having a carboxyl group or a salt thereof, such as styrenesulfonic acid and a salt thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); acrylamide, methacrylamide, N-alkyl acrylamide , N-alkyl methacrylamide, N,N-dialkyl acrylamide, N,N-dialkyl methacrylamide (alkyl such as methyl, ethyl, n-propyl, isopropyl Base, n-butyl, isobutyl, 3-butyl, 2-ethylhexyl, cyclohexyl, etc.), acryloylmorpholine, N-methylol acrylamide, N-methylolmethacryl Guanamine, N- a monomer having a mercaptoamine group such as phenylacrylamide or N-phenylmethacrylamide; an anhydride monomer such as maleic anhydride or itaconic anhydride; vinyl isocyanate, allyl isocyanate, styrene, Vinyl methyl ether, vinyl ethyl ether, vinyl trialkoxy decane, alkyl maleic acid monoester, alkyl fumaric acid monoester, alkyl itaconic acid monoester, acrylonitrile, methacrylonitrile, chlorine Vinyl, ethylene, propylene, vinyl chloride, vinyl acetate, butadiene, etc., are not limited by these.

The content of the polyester resin (P) forming the adhesion-promoting coating in the adhesion-promoting coating layer is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight. The content ratio of the azozoline group and the polyoxyalkylene chain-containing acrylic resin (Q) forming the adhesion-promoting coating layer in the adhesion-promoting coating layer is preferably from 5 to 90% by weight, more preferably from 10 to 50% by weight. good. When the polyester resin (P) is more than 95% by weight, or the acrylic resin (Q) having an oxazoline group and a polyoxyalkylene chain is less than 5% by weight, the cohesive force of the adhesion-promoting coating is lowered, and the transparent conductive film is formed. The adhesion of the layers is insufficient.

In order to form an adhesion-promoting coating on the base film, it is preferred to use an aqueous coating liquid in which the above components are formed into an aqueous solution, an aqueous dispersion or an emulsion. In order to form a film, other components other than the above components may be added as needed, such as an antistatic agent, a colorant, a surfactant, an ultraviolet absorber, and the like. In particular, by adding a smoothing agent, the blocking resistance can be improved.

The solid content concentration of the aqueous coating liquid used for coating the tackifying coating layer is usually 20% by weight or less, particularly preferably 1 to 10% by weight. When the ratio is less than 1% by weight, the wettability to the base film is insufficient, and when it is more than 20% by weight, the storage stability of the coating liquid or the appearance of the tackifying coating may be deteriorated.

The film thickness of the adhesion-promoting coating layer is not particularly limited insofar as it has a sufficient effect of improving the adhesion and does not impair the transparency. The film thickness of the adhesion-promoting coating layer is preferably 0.001 to 0.10 μm, more preferably 0.005 to 0.090 μm, and most preferably 0.01 to 0.085 μm.

The coating method for forming the tackifying coating layer may be a method known per se. For example, the slit direct coating method, the vertical mold coating method, the slit reversible method, the mold coating method, the gravure roll coating method, the distributed coating method, the spray coating method, the air knife coating method, the dip coating method, the rod coating method, and the like are preferred. . These methods can be used alone or in combination. Further, depending on the desired film, it may be formed only on one side of the film or on both sides.

In the conductive film of the present invention, it is necessary to laminate the above-mentioned film layer on at least one side of the base film, and to provide a tackifying coating, a hard coating layer, etc., depending on the surface on which the film layer is formed. The film.

(physical properties of conductive film)

The rate of change in surface resistance of the conductive film of the present invention after treatment at a temperature of 60 ° C and a humidity of 90% for 240 hours is 160% or less, preferably 150% or less. When the rate of change is more than 160%, the environmental resistance is insufficient, and it is difficult to use it for a long time. The rate of change can be easily adjusted by appropriately setting the amount of the water-soluble compound (component B) or the crosslinking agent (component C). The conductive film of the present invention has a total light transmittance of 60% or more, preferably 65%. The above is better, preferably 70% or more, and 80% or more. The total light transmittance was measured in accordance with JIS K 7150. A transparent electrode or an electromagnetic wave sealing material which is a liquid crystal display device, a transparent touch panel or the like can be suitably used by satisfying the requirement of the total light transmittance. The total light transmittance can be adjusted by appropriately setting the film thickness of the base film or the film layer.

Further, the surface resistivity of the coating layer of the conductive film of the present invention is preferably 10 to 1 × 10 ⁴ Ω/□, more preferably 10 to 5 × 10 ³ Ω/□. When the surface resistance is in this range, it is preferable to use an electrode or a electromagnetic wave sealing property as a transparent electrode or an electromagnetic wave sealing material such as a liquid crystal display device or a transparent touch panel.

(Form 1)

In the present invention, a preferred conductive film is, for example, the following.

Conductive polymer (component A) containing (i) a polycationic polythiophene containing a repeating unit represented by formula (1) and a polyanion, (ii), at least one surface of the base film, (ii) 10 to 1,000 parts by mass of 100 parts by mass of the A component contains 3 or more photocurable functional groups and oxyethylene groups (-O-CH ₂ -CH ₂ -) in the molecule, and the total number of oxyethylene groups is 10 to 30 of the water-soluble compound (component B-1), and (iii) 10 to 1,000 parts by mass of the epoxy group-containing alkoxydecane compound (component C-1) for 100 parts by mass of the component A The film layer which has been cured by the composition is preferably subjected to a treatment at a temperature of 60 ° C and a humidity of 90% for 240 hours, and the rate of change in surface resistance is preferably 150% or less.

The A component, the B-1 component, and the C-1 component are as described above.

The photocurable functional group of the component B-1 is preferably a (meth) acrylate group.

The compound represented by the above formulas (2) to (4) is preferred as the component B-1.

The content of the B-1 component is 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the conductive polymer (component A).

The component C-1 is preferably a trialkoxy decane having a glycidoxy group. Among them, γ-glycidoxypropyltrimethoxydecane is preferred. The content of the component C-1 is 10 to 1,000 parts by mass, preferably 20 to 300 parts by mass, and more preferably 30 to 200 parts by mass, per 100 parts by mass of the conductive polymer (component A).

The conductive film preferably has a total light transmittance of 60% or more and a surface resistance of 10 to 1 × 10 ⁴ Ω/□. It is preferred to have a tackifying coating layer having a polyester resin and an oxazoline group and a polyoxyalkylene chain-containing acrylic resin between the substrate film and the film layer. The base film is preferably a polyethylene terephthalate or polyethylene naphthalate dicarboxylate film.

(Form 2)

In the conductive film of the present invention, a conductive polymer containing (i) a polycationic polythiophene containing a repeating unit represented by the formula (1) and a polyanion containing at least one of the repeating units represented by the formula (1) is laminated on at least one surface of the base film. (Part A), (ii) 25 to 55 parts by mass of a water-soluble polyester (B-2 component) having a sulfonate group and a hydroxyl group or a carboxyl group per 100 parts by mass of the component A, and (iii) 100 parts by mass A component: 10 to 1,000 parts by mass of an alkoxydecane compound having an epoxypropyl group (component C-1), and 1 to 16 parts by mass of an acrylic modified polyester having an epoxypropyl group (component C-2) The film layer to be cured is preferably subjected to a treatment at a temperature of 60 ° C and a humidity of 90% for 240 hours, and the rate of change in surface resistance is preferably 160% or less.

The total light transmittance is 80% or more, and the surface resistance is preferably 10 Ω/□ or more and 1 × 10 ⁵ Ω/□ or less. The base film is preferably a polyester film.

The A component, the B-2 component, the C-1 component, and the C-2 component are as described above.

The component B-2 is a polyester formed of a dicarboxylic acid component and a diol component. The component B-2 contains a sulfonate group. The sulfonate group is an alkali metal salt group of a sulfonic acid represented by -SO ₃ Na or -SO ₃ K. The content of the sulfonate group in the component B-2 is preferably from 2 to 10 mol%, more preferably from 5 to 8 mol%, based on the total acid component of the 100 mol% B-2 component. The component B-2 contains a hydroxyl group, a carboxyl group or both. The total content of the hydroxyl group or the carboxyl group is preferably from 0.1 to 40 mol%, more preferably from 1 to 20 mol%, based on the total acid component of the 100 mol% B-2 component.

The content of the component B-2 in the composition is preferably from 25 to 55 parts by mass, more preferably from 30 to 55 parts by mass, based on 100 parts by mass of the conductive polymer (component A), and the optimum is 35. ~55 parts by mass.

An acrylic modified polyester (C-2 component) having a glycidyl group, which is self-crosslinkable by containing a glycidyl group, and reacts with a hydroxyl group or a carboxyl group of a water-soluble polyester (component B-2). As a function of the crosslinking agent. The content of the epoxy propyl group is preferably from 3 to 20 mol%, more preferably from 5 to 15 mol%, based on 100 parts by mole of the acrylic component of the C-2 component. By containing both the C-1 component and the C-2 component, it is possible to maintain conductivity and obtain a conductive film excellent in moist heat resistance.

(touchpad)

In the resistive film type touch panel in which one of the conductive layers is provided with the counter electrode via the spacer and the conductive layer is disposed opposite to each other, it is preferable that the conductive film of the present invention is used for at least one of the electrodes.

In the following, the invention will be more specifically described by way of examples. Parts in the examples mean parts by mass. Each evaluation in the examples was carried out in the following manner.

(1) Film thickness

The thickness of the adhesion-promoting coating layer and the coating layer is measured by a reflection spectroscopic film thickness meter (manufactured by Otsuka Electronics Co., Ltd., trade name "FE-3000"), and the reflectance at a wavelength of 300 to 800 nm is measured, and n-k Cauchy is cited. Dispersion is a similar form of wavelength dispersion of a typical refractive index, and the film thickness is obtained by the measured value and the coincidence value of the spectrum.

(2) Surface resistance

The Lorester MCP-T600 manufactured by Mitsubishi Chemical Corporation was used and measured in accordance with JIS K 7194. The measurement system measures any of the five places, and the average value of these is obtained.

(3) Surface resistance change rate

The sample for measuring the surface resistance was placed in a constant temperature and humidity chamber at 60 ° C × 90%, and after treatment for 240 hours, the surface resistance was measured, and the surface resistance change rate was obtained by the following formula.

Surface resistance change rate (%) = (surface resistance after treatment / surface resistance before treatment) × 100

The smaller the change rate of the surface resistance shown by the formula is, the better the heat and humidity resistance is.

(4) Total light transmittance

The measurement was carried out by using a haze meter HCM-2B manufactured by Sika (transliteration tester) as a reference based on JIS K7150.

(5) Film strength (film adhesion)

The measurement was carried out using a vibration vibration tester (manufactured by Di Shita Co., Ltd., trade name: Xue Zhen type friction fastness tester). Specifically, when a load of 700 g was sufficiently applied to a gauze of 10 mm ² , the peeling state of the film was evaluated by applying a load of 700 g to the film at a speed of 1 round/back/2 seconds. The evaluation results are as follows.

○: The film was not peeled off △: It was peeled off and the film remained. ×: It was completely peeled off, and no film remained.

[Examples] Example 1

<Formation of Substrate Film and Adhesive Coating Layer> The molten polyethylene terephthalate ([η]=0.62 dl/g, Tg=78 ° C) was extruded by a mold, and the cooling barrel was cooled by a conventional method. The mixture was cooled to form an unstretched film, and then stretched 3.4 times in the longitudinal direction, and then coated on both sides to form a coating liquid composed of 60 parts of the following polyester, 30 parts of acrylic acid, 5 parts of an additive, and 5 parts of a wetting agent. The coating liquid for the adhesion-promoting coating layer adjusted to a concentration of 8% by ion-exchanged water was uniformly coated by a roll coating method. Then, after coating, the film was stretched 3.6 times in the transverse direction at 125 ° C, and heat-fixed by shrinking 3% in the width direction at 220 ° C to form an adhesion-promoting coating to obtain a substrate film having a thickness of 188 μm. . Moreover, the thickness of the adhesion-promoting coating was 0.04 μm.

<Component of coating liquid for adhesion-promoting coating> Polyester: acid component is 2,6-naphthalenedicarboxylic acid 65 mol%/isophthalic acid 30 mol%/5-sodium sulfoisophthalic acid 5 The molar % and the alcohol component were composed of ethylene glycol 90 mol % / diethylene glycol 10 mol % (Tg = 80 ° C, number average molecular weight Mn = 13,000).

In addition, this polyester is manufactured as follows based on the method described in Example 1 of JP-A-6-116487. In other words, 44 parts of dimethyl 2,6-naphthalenedicarboxylate, 4 parts of dimethyl isophthalate, 34 parts of ethylene glycol, 2 parts of diethylene glycol, and 0.05 parts of four were added to the reactor. Titanium butoxide was heated under a nitrogen atmosphere to control the temperature at 230 ° C, and the produced methanol was distilled off to carry out a transesterification reaction. Then, the temperature of the reaction system was gradually raised to 255 ° C, and the internal pressure was reduced to 1 mmHg to carry out a polycondensation reaction to obtain a polyester.

Acrylic acid: methyl methacrylate 30 mol%/2-isopropenyl-2-oxazoline 30 mol%/polyethylene oxide (n=10) methacrylate 10 mol%/acrylamide 30 Mole % is composed (Tg = 50 ° C).

In addition, the acrylic resin is produced as follows based on the method described in Production Examples 1 to 3 of JP-A-63-37167. In other words, 3 parts of sodium lauryl sulfonate as a surfactant and 181 parts of ion-exchanged water were added to a four-necked flask, and the temperature was raised to 60 ° C in a nitrogen gas stream, and then 0.5 part of ammonium persulfate of a polymerization initiator was added, 0.2. Part of sodium hydrogen nitrite, and then add 23.3 parts of monomeric methyl methacrylate and 22.6 parts of 2-isopropenyl-2-oxazoline to the liquid temperature at 60-70 ° C within 3 hours. 40.7 parts of a mixture of polyethylene oxide (n=10) methacrylic acid and 13.3 parts of acrylamide. After the completion of the dropwise addition, the reaction was continued for 2 hours in the same temperature range with stirring, and then cooled to obtain an aqueous dispersion of acrylic acid having a solid content of 35%.

Additive: cerium oxide filler (average granule 100nm) (Nissan Chemical Co., Ltd.: trade name Strodigus (transliteration) ZL)

Wetting agent: Polyethylene oxide (n=7) lauryl ether (Sanyo Chemical Co., Ltd. product name Nami Yagudi (transliteration) N-70)

<Formation of Coating Layer> To 97 parts of a conductive polymer containing 0.5% by weight of poly(3,4-vinyl thiophene) and 0.8% by weight of polystyrenesulfonic acid (number average molecular weight Mn = 150,000) In the case of an aqueous dispersion (by Bayeru AG, trade name BaytronP), 3 parts of diethylene glycol, 0.5 part of γ-glycidoxytrimethoxydecane (C1), and 0.38 parts are used as water-soluble compounds ( B1) A-GLY-20E (new) Nakamura Chemical Industry Co., Ltd., having the structure shown by formula (2), l+m+n=20), 0.015 parts as a photopolymerization initiator, Rukachia 184 ( After mixing, the coating liquid was stirred for 1 hour, and coated on a base film provided with the above-mentioned adhesion-promoting coating using a Meyer rod, and dried at 140 ° C for 1 minute, and then continuously subjected to 300 mJ. UV irradiation of /cm ² produces a conductive film having a coating layer. The thickness of the coating layer was 0.08 μm. The properties of the obtained conductive film are shown in Table 1.

Example 2

The same procedure as in Example 1 was carried out except that 0.38 parts of AT-20E (manufactured by Shin-Nakamura Chemical Co., Ltd., having the structure represented by the formula (3), and l+m+n=20) was used as the water-soluble compound (B2). The results are shown in Table 1.

Example 3

The same procedure as in Example 1 was carried out except that 1.14 parts of A-GLY-20E (manufactured by Shin-Nakamura Chemical Co., Ltd., having the structure represented by the formula (2), and l+m+n=20) was used as the water-soluble compound (B1). . The results are shown in Table 1.

Example 4

The same procedure as in Example 1 was carried out except that 0.75 parts of γ-glycidoxytrimethoxydecane (C1) was used. The results are shown in Table 1.

Example 5

The same procedure as in Example 1 was carried out except that 1.0 part of γ-glycidoxytrimethoxydecane (C1) was used. The results are shown in Table 1.

Modulation example 1

97 parts of an aqueous dispersion containing 0.5% by mass of poly(3,4-ethylene thiophene) and 0.8% by mass of polystyrenesulfonic acid (number average molecular weight Mn = 150,000) (by Bayeru AG, trade name: Baytron P) was mixed as a conductive polymer with 3 parts of diethylene glycol and 0.5 part of γ-glycidoxytrimethoxydecane (C1), and stirred for 1 hour to obtain a dispersion. To the obtained dispersion, 1.8 parts of a water-soluble polyester (B3, manufactured by Mutual Chemical Co., Ltd., trade name: Braskton RZ-570 (solid content: 25 mass%)) was added, and the mixture was stirred for 15 minutes. Get a mixture. The content of the water-soluble polyester (B3) in the mixed liquid is 36 parts by mass based on 100 parts by mass of the conductive polymer.

The RZ-570-based dicarboxylic acid component is composed of terephthalic acid (80 mol%), isophthalic acid (14 mol%), and 5-Nasulfoisophthalic acid (6 mol%). The alcohol component is a water-soluble polyester composed of ethylene glycol (74 mol%), diethylene glycol (8 mol%), and hexamethylene glycol (18 mol%). RZ-570 fat has a weight average molecular weight of 23,000.

Modulation example 2

The same operation as in Preparation Example 1 was carried out except that 2.4 water-soluble polyesters (B3, manufactured by Mutual Chemical Co., Ltd., trade name: Blasqueston RZ-570 (solid content: 25 mass%) were used to prepare a mixed liquid. The content of the liquid water-soluble polyester (B3) is 48 parts by mass based on 100 parts by mass of the conductive polymer.

Example 6

To the mixed solution obtained in Preparation Example 1, 0.2 part of an acrylic modified polyester having a glycidyl group (C2, manufactured by Takamatsu Oil Co., Ltd., trade name: Bethley A-615GE (solid content: 25 mass%)) was added. Stirring was carried out for 15 minutes to prepare a coating liquid.

The obtained coating liquid was coated on the base film provided with the adhesion-promoting coating layer of Example 1 using a Meyer rod, and then dried at 140 ° C for 1 minute to obtain a coating having a film thickness of 100 nm. A conductive film of the film. The content of the epoxy acrylate-modified acrylic polyester (C2) in the coating layer is 4 parts by mass based on 100 parts by mass of the conductive polymer. The above various measurements were carried out on the obtained conductive film. The results are shown in Table 1.

Bass resin A-615GE, which has methyl methacrylate (225 mol%) and glycidyl methacrylate (17 mol%) for a 100 mol% polyester dicarboxylic acid component. Acrylic modified polyester. The epoxy propyl group is 7 mole % for the 100 mole % acrylic component. Here, the polyester dicarboxylic acid is terephthalic acid (55 mol%), isophthalic acid (40 mol%), 5-Nasulfoisophthalic acid (5 mol%), diol The ingredients were ethylene glycol (77 mol%) and diethylene glycol (23 mol%). The number average molecular weight of the Bass resin A-615GE is 7,700, the number average molecular weight of the polyester component is 3,500, and the number average molecular weight of the acrylic component is 4,200.

Example 7

In addition to 0.4 parts of the acrylic acid-modified polyester (C2, manufactured by Takatsuki Oil Co., Ltd., trade name: Beth resin A-615GE (solid content: 25 mass%)), which was added to the mixed liquid obtained in the preparation example 1, A conductive film having a coating layer was obtained by the same operation as in Example 6 except that the mixture was stirred for 15 minutes. Further, the content of the acrylic modified polyester (C2) having a glycidyl group in the coating layer is 8 parts by mass based on 100 parts by mass of the conductive polymer. The measurement results of the characteristics of the obtained conductive film are shown in Table 1.

Example 8

In addition to 0.8 parts of the acrylic acid-modified polyester (C2, manufactured by Komatsu Oil Co., Ltd., trade name: Bass resin A-615GE (solid content: 25 mass%)), which was added to the mixed liquid obtained in the preparation example 1, A conductive film having a coating layer was obtained by the same operation as in Example 6 except that the mixture was stirred for 15 minutes. Further, the content of the acrylic modified polyester (C2) having a glycidyl group in the coating layer is 16 parts by mass per 100 parts by mass of the conductive polymer. The measurement results of the characteristics of the obtained conductive film are shown in Table 1.

Example 9

A conductive film having a coating layer was obtained by the same operation as in Example 6 except that the mixed solution obtained in Preparation Example 2 was used. The measurement results of the characteristics of the obtained conductive film are shown in Table 1.

Comparative example 1

A conductive film having a coating layer was obtained by the same operation as in Example 1 except that only the mixed liquid obtained in Preparation Example 1 was coated. The measurement results of the characteristics of the obtained conductive film are shown in Table 1.

[effect of the invention]

The conductive film of the present invention is excellent in moist heat resistance. Further, the conductive film of the present invention is excellent in conductivity, transparency, and film strength. Since the conductive film of the present invention can maintain transparency and conductivity and has excellent moist heat resistance, it can be used stably for a long period of time when it is used for an electrode for a display device or an electrode for a touch panel.

[industrial use value]

The conductive film of the present invention is used as a touch panel, a liquid crystal display device (LCD), an organic electroluminescent element (OLED), an inorganic electroluminescence field because it can maintain excellent conductivity and has high heat and humidity resistance. A transparent electrode or an electromagnetic wave sealing material such as a component is extremely useful.

1. . . Substrate film

2. . . Viscosity-coated coating

3. . . Coating

4. . . Hard coating

Fig. 1 is a cross-sectional view showing an example of a conductive film of the present invention.

2. . . Viscosity-coated coating

3. . . Coating

4. . . Hard coating

Claims (7)

A conductive film characterized in that a film layer is laminated on at least one surface of a base film, and the film layer is formed by curing a composition containing the following (i) to (iii); (i) comprising the following a conductive polymer (A component) of a polycationic polythiophene and a polyanion having a repeating unit represented by the formula (1), In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or an alkylene group having 1 to 12 carbon atoms which may be optionally substituted, and (ii) 100 parts by mass of A. 10 to 1,000 parts by mass of a water-soluble compound (component B) having at least one hydrophilic group selected from the group consisting of oxyethylene groups and sulfonate groups, wherein the component B contains 3 molecules in the molecule. The above-mentioned photocurable functional group and oxyethylene group, and the total number of oxyethylene groups is 10 to 30 water-soluble compounds (component B-1), and (iii) 10 to 1,000 parts by mass for 100 parts by mass of component A. The crosslinking agent having a glycidyl group (component C); and the rate of change in surface resistance after the conductive film was treated at a temperature of 60 ° C and a humidity of 90% for 240 hours was 160% or less. A conductive film characterized in that a film layer is laminated on at least one surface of a base film, and the film layer is formed by curing a composition containing the following (i) to (iii); (i) comprising the following a conductive polymer (A component) of a polycationic polythiophene and a polyanion having a repeating unit represented by the formula (1), In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or an alkylene group having 1 to 12 carbon atoms which may be optionally substituted, and (ii) 100 parts by mass of A. The component contains 10 to 1,000 parts by mass of a water-soluble compound (component B-1) having three or more photocurable functional groups and an oxyethylene group in the molecule and having a total number of oxyethylene groups of 10 to 30 ( Iii) 10 to 1,000 parts by mass of the alkoxydecane compound having an epoxypropyl group (component C-1) for 100 parts by mass of the component A; and the conductive film is treated at a temperature of 60 ° C and a humidity of 90%. The rate of change in surface resistance after an hour is 150% or less. The conductive film of claim 1 or 2, wherein the photocurable functional group is a (meth) acrylate group. For example, in the conductive film of claim 1 or 2, the total light transmittance is 60% or more, and the surface resistance is 10 to 1 × 10 ⁴ Ω/□. The conductive film of claim 1 or 2, wherein a thickening coating is provided between the substrate film and the coating layer, the adhesion promoting coating comprising a polyester resin, and having an oxazoline group and a poly An alkylene oxide chain acrylic resin. The conductive film of claim 1 or 2, wherein the substrate film is a polyethylene terephthalate or a polyethylene naphthalate dicarboxylate film. A touch panel is a resistive film type touch panel in which a pair of conductive layers are disposed via a spacer and a conductive layer is disposed opposite to each other, and is characterized in that at least one of the electrodes is used as claimed in the patent scope A conductive film of any one of items 1 to 6.